Whole protein shampoo composition

ABSTRACT

A shampoo is prepared by incorporating into a shampoo base a whole protein composition obtained by solubilization of a keratin protein material particularly chicken feathers, and an alkanolamine, such as triethanolamine, or with N,Ndimethylformamide, and a surfactant.

llnite States atent [191 Goodwin WHOLE PROTEIN SHAMPOO (IOMPOSITION [75]Inventor: William D. Goodwin, Decatur, Ga.

[73] Assignee: The Atltlon Corporation, Atlanta,

[22] Filed: Oct. 22, 1971.

[21] Appl. N0.: 191,780

[56] References Cited UNITED STATES PATENTS 2,447,860 8/1948 Jones etal. 260/123] OTHER PUBLICATIONS Protein Derived Detergents, Soap andChemical Specialties, May 1963, Riso, pp. 82-84, 151, 153, 155, 157 and158.

The Chemical Formulary, H. Bennett, 1968, p. 123.

Primary ExaminerHerbert B. Giuynn Assistant Examiner-Bruce H. HessAttorney, Agent, or Firm-Edmund M. Jaskiewicz [5 7 ABSTRACT A shampoo isprepared by incorporating into a shampoo base a whole proteincomposition obtained by so]- ubilization of a keratin protein materialparticularly chicken feathers, and an alkanolamine, such astriethanolamine, or with N,N-climeth.ylformamide, and a surfactant.

11 Claims, No Drawings WIHIQLlE PROTIEHN SHUU CUMPUSHTTQN BACKGROUND orTHE INVENTION It has long been recognized that a shampoo should possessnot only adequate cleansing action on the hair and scalp, but shouldalso leave the hair in manageable and attractive condition. The use ofproteinaceous additives in shampoos is well known in the prior art, butthe additives which have been proposed heretofore for this purpose haveall been protein hydrolysates, such as, for example, those derived fromcollagen protein. This type of protein represents a material foreign tothe keratinaceous protein of the hair. Moreover, there is norelationship between the peptide units present in collagen and thoseoccurring in hair itself. Accordingly, what has been lacking has been aprotein type additive which would be analogous in composition to hairitself and which would retain the primary and secondary states of thenatural protein from which it is derived, rather than be composed ofhydrolysis or degradation products.

GENERAL DESCRIPTION OF THE TNVENTION In accordance with the presentinvention, there is provided a novel whole protein composition adaptedfor incorporation into a shampoo base, and a novel shampoo compositionprepared therefrom.

The whole protein additive of the invention is composed of components ofkeratinaceous materials soluble in either N,N-dimethylformamide, or inan alkanolamine, such as triethanolamine.

The solubilized protein represents an unhydrolyzed product, in which thekeratin proteins which are extractable retain their original undegradedcondition. The whole protein is combined with suitable surfactants,emollients, perfumes, and other conventional shampoo ingredients toprovide novel shampoo compositions which are more beneficial to the hairthan those known heretofore. The whole protein additive of the inventionis capable of supplying nutrients analogous in composition to thekeratinaceous hair protein itself.

A source of keratinaceous protein which has proved especially suitablefor the purposes of the invention is avian feathers. It is known tohydrolyze keratinaceous materials such as poultry feathers and the likeby the use of alkalis such as strontium hydroxide, to produce ahydrolysate having a high content of the amino acids cystine, tyrosineand tryptophane, which is said to be suitable for cosmetic use, and aprocess of this type is disclosed, for example, in Us. Pat. No.1,974,544. It is also known to extract water soluble materials from akeratin structure such as animal horns, hair, hoofs, and the like, usingvarious water-miscible polar solvents including alcohols and ketones, toobtain extracts adapted for topical use on human skin.

The poultry processing industry operates on a scale which results in theproduction of large tonnages of byproduct keratinaceous materials,principally feathers, which are sold as feather meal. The presentinvention provides a new use for this by-product material. Whilefeathers of various domestic fowl, such as chickens, ducks, and turkeysmay be used, the invention will be described with regard to thetreatment of chicken feathers, it being understood that its scope is notto be considered as limited thereby.

In accordance with the invention, a whole protein composition suitableas an ingredient of shampoos is obtained from avian keratinaceousmaterial, such as chicken feathers, with an alkanolamine or withN,N-dirnethylformamide or an aqueous solution thereof, for a sufficienttime to solubilize and extract a whole protein composition therefrom,and then separating the protein extract from the insoluble residue, andrecovering the protein composition from the extract.

N,N-dimethylformamide (DMF) is a liquid, b. pt. 153C, sp. gr. 0.945,which is miscible with water, and has been used heretofore principallyas a solvent for polymeric materials. So far as known, it has not beenused, prior to the present invention, as a medium for the solubilizationof proteinaceous materials. In fact, both casein and gelatin arereported to be insoluble in DMF.

The alkanolamines which may also be employed as solubilizers forkeratinaceous materials include the ethanolamines, examples of which aremonoethanolamine, diethanolamine, and triethanolamine. Triethanolamine(TEA) is preferred. This compound is a liquid, b. pt. 360C, sp. gr.1.126. Aqueous solutions of the alkanolamines may also be employed.

It was both surprising and unexpected to discover that dimethylforamideand triethanolamine and their aqueous solutions act as a solvent for theprotein of avian feathers, to yield a whole protein which is of value asan ingredient of shampoos.

Either the DMF or the -TEA may be employed in 100% concentration, or inadmixture with water. In the case of the DMF, the aqueous solutionshould contain not less than about DMP by weight. The ethanolamines arepreferably employed without dilution.

The proportion of extractant to feathers will ordinarily range betweenabout 15 and about 30 parts DMF basis) per part of feathers, by weight.For the ethanolamines, the proportion ranges between about and about 300parts by weight of feathers per 1,000 parts ethanolamine by volume.

While whole feathers and their associated parts, including quillportions, may be treated in their removed condition, advantageously thefeathers including quill portions are crushed prior to contacting themwith the DMF or DlVlF solution, or the ethanolamine.

The solubilization may be performed at atmospheric or superatmosphericpressure, but; preferably it is carried out at atmospheric pressure. Thetemperature of the extraction will generally correspond to the chosenpressure, but for the purposes of the invention, the extraction ispreferably carried out by contacting the feathers with boiling DlVlF orDMF solution or with an ethanolamine at elevated temperature usuallybelow the boiling point, at atmospheric pressure. Advantageously this isdone by introducing the feathers, which may be crushed, into a body ofthe solvent, in a vessel equipped with a reflux condenser.

The treatment time will depend. upon the nature of the feathers, theconcentration of the extractant, and the extent to which the solvationis to be carried, as well as the usual parameters of temperature andpressure. in general the time is of the order of about 4 to 8 hours,although the time can be extended to 20 hours or more. However, suchextended treatment periods do not significantly increase the yield ofextracted proteinaceous component, and thus the time interval chosendepends upon economic considerations. The use of aqueous DMF solutionsmay be preferable to that of pure DMF, since the latter may sometimesfurnish a product slightly darker in color.

When the solubilization step is complete, the hot solution is separatedfrom the insoluble feather material by any suitable method, as byfiltration or centrifuging. The clarified solution is cooled to ambienttemperature, and forms a gel.

The insoluble residue may be further extracted with the solvent toobtain additional protein.

The process of solubilization of the avian feather proteins, inaccordance with the invention, is to be distinguished from hydrolyses,such as those known heretofore. The process of the invention results inthe production of a whole protein. While not wishing to be bound by anyparticular theory, it is believed that in the treatment withdimethylformamide or an ethanolamine, the keratinaceous constituents ofthe feathers, which possess a quaternary structure are broken up torelieve the stresses in the long chain molecules. In the keratinaceousstate, the quaternary structure of the protein is due largely tosecondary valence bond forces. Compared with a primary valence bondthese secondary forces are individually extremely weak but they arenevertheless significant because of the large number present. Breakingthese secondary valence forces results in loss of quaternary structureresulting in solubilization. The direct production or even destructionof amino acids which is characteristic of acid or alkaline hydrolytictreatments is thus avoided or minimized by the use of extracts of theinvention, whereby a whole protein product representing only a break-upof long chain molecules is obtained.

The protein can be extracted and altered from keratinaceous tissues by anumber of applications of the DMF solvent by progressively longerperiods of refluxing and/or progressively higher temperatures. Eachsuccessive extraction yields protein of lower gelling strength andviscosity. Since a higher proportion of protein is extracted in theearly treatment of the keratin the proportion of high protein value ismuch greater than in the later treatments.

A typical analysis of the dried whole protein, as obtained from chickenfeathers in terms of amino acid equivalents, is as follows:

AMINO ACID ANALYSIS OF PROTEIN Based on Sample as 100% protein Microninle per milligram of protein In accordance with one aspect of theinvention, the whole protein obtained by cooling of the clarifiedN,N-dimethylformarnide (DMF) extract may be dried by any suitable means,recovering the solvent, which is then recycled. The recovered wholeprotein material may be subsequently admixed with surfactants and otheringredients to form a shampoo. In such case, the solution isconcentrated by evaporating the solvent to a point where the proteincontent reaches 65% by weight or higher. Care must be exercised to avoidoverheating as the solvent content approaches minimal values. Theprotein may be dried by spray drying technique by passing the materialunder pressure through a tungsten discharge nozzle into a stainlesssteel chamber maintained at atmospheric pressure, into which dry air isintroduced at a temperature of about 400F, the air being withdrawn fromthe chamber at about 240F, but these temperatures are merelyillustrative, and may be varied within wide limits. This drying stepalso serves to volatilize the solvent which is condensed and recovered.The proteinaceous product is a dry powder without any vestige of DMF,light in color, having a particle size averaging about 2 mils orslightly larger, the particles being crystalline in appearance. Theproduct has a pH of about 7 and is nontoxic.

Another method of drying employs drum dryers or fiakers whereby theproduct is fed between two heateddrums rotating in opposite directionssuch that the wetted surfaces display their evaporating film coating onthe periphery of the drums untouched until reaching the stripping bladeswhere the dried film is removed in the form of flakes.

In accordance with a preferred aspect of the invention, the wholeprotein product is not separated and dried, however, but is allowed toremain in the solvent in the form of a concentrated solution, but in aform capable of being admixed with or combined with a surfactant, and/orother shampoo ingredients to provide a shampoo base.

In the case of DMF extract, a detergent or surfactant material is addedwith vigorous agitation to provide desirable properties of sudsing orlathering, viscosity, and protein buffering.

Alternatively, and particularly in the case of an ethanolamine extract,an anionic component may be added which will react with the ethanolaminepresent to form an ethanolamine salt having detergent or surfactantproperties. Thus, for example, a compound having detergent properties,such as lauryl hydrogen sulfate, may be added to a triethanolamineextract until the solution has been neutralized, thereby forming thesurfactant triethanolamine lauryl sulfate in situ, the whole proteincomponent remaining in solution, to form a shampoo base of completelynovel character. The same type of reaction may be utilized to formsurfactants in the solution with the acidic components of otheranion-active detergent components. The concentration may be adjusted tocorrespond with the amount of the ethanolamine solvent which remains inthe extract, and will generally be between about 1% and about 10% ofsurfactant by weight.

Where the surfactant is not formed in situ, but is to be added to thewhole protein ingredient of the shampoo, the blending of the ingredientsmay take place in accordance with conventional shampoo preparationpractice. The surfactants may be cation-active, such as quaternaryammonium salts and esters, for example, stearyl trimethyl ammoniumchloride, coco dimethyl benzyl ammonium chloride, and the like; oranionactive, such as sodium lauryl sulfate; or nonionic, such aspolyoxyethylene sorbitan mono-oleate, polyoxyethlene glycolmonopalmitate, and the like.

If desired the shampoo of the invention may be prepared in pressurizedemulsion or aerosol form, using a pressurized gas such as nitrous oxide,or a fluorinated hydrocarbon such as dichlorodifluoromethane as apropellant.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The following examplesillustrate the practice of the invention, but are not to be regarded aslimiting:

EXAMPLE 1 One hundred fifty g of chicken feathers, 1,500 mlN,N-dimethylformamide and 500 ml water are refluxed at 100C for 20 hoursin a threenecked flask equipped with a reflux condenser at atmosphericpressure. lnsoluble feather material is separated from the hot reactionmixture by filtration. The clarified solution is evaporated to a volumeof 275 ml, forming a concentrate having a protein content of 65% byweight, equivalent to a yield of 82%, representing the removal ofvirtually all the DME originally present. Sodium lauryl sulfatesurfactant in an amount of about 15g (400 ml aqueous solution) is addedto the hot protein concentrate with vigorous stirring. Perfume,coloring, and preservatives are then added in conventional amounts toyield a liquid shampoo, e.g., 0.15 part preservative, 0.05 partcoloring, and 0.5 part perfume.

EXAMPLE 2 One thousand fifty ml triethanolamine are added to a oneliter, three neck flask equipped with reflux condenser, gas inlet tubeand stirrer. The TEA is heated to 170C under a nitrogen atmosphere toretard oxidation. 175 g chicken feathers are added in 25 g portions overa period of 1 hour. The solution is then heated for a period of 4 hoursat 170C after which time there was no evidence of insoluble material.The solution is then filtered while hot to remove any possibleextraneous matter and allowed to cool, yielding a brown viscous producthaving a pH 9.3, suitable for the preparation of a shampoo base.

Three hundred ml of the material thus obtained is diluted with 50 mlwater. The pH is adjusted to 7.5 by the addition of lauryl hydrogensulfate in a fine stream with constant stirring and cooling. On standingfor hours the solution becomes quite viscous and free from cloudiness.The product is suitable as a shampoo concentrate and can be diluted withwater to yield a high lathering, nonirritating shampoo which hasexcellent cleansing properties.

EXAMPLE Il temperature of 145C for 2 hours. The resulting hot brownviscous liquid is filtered through a cotton pad. The refractive index ofthe final solution is 1.493 at 25C. The solution represents aconcentration of 27% w/v based on complete solubilization of thefeathers. A higher concentration becomes progressively more difficult tofilter. The product is worked into a shampoo base as described inExample 2.

What is claimed is:

l. An aqueous shampoo composition consisting essentially of a wholeundegraded protein component of avian feathers sufficient to impartmanageability to hair, said protein component being extracted byN,N-dirnethylforrnamide, a detergent surfactant selected from the groupconsisting of a cation-active surfactant, a anion-active surfactant. anda nonionic surfactant to provide sudsing or lathering properties, andWater.

2. The composition of claim 1 in which the avian feathers are poultryfeathers.

3. The composition of claim 11 in which the avian feathers are chickenfeathers.

41. An aqueous shampoo composition consisting essentially of a wholeundergraded protein component of avian feathers sufficient to impartmanageability to hair, said protein component being soluble in a memberselected from the group consisting of an ethanolamine andN,N-dimethylformamide, a detergent surfactant selected from the groupconsisting of a cationactive surfactant, a anion'active surfactant and anonionic surfactant to provide sudsing or lathering properties, andwater.

5. The composition of claim 4 in which the avian feathers are poultryfeathers.

6. The composition of claim 4i in which the avian feathers are chickenfeathers.

7. The composition of claim 4 in which the ethanolamine istriethanolamine.

8. The composition of claim 4 in which the surfactant istriethanolarnine lauryl sulfate.

9. Method for the preparation of a shampoo concentrate comprising thesteps of treating avian feathers with a solubilizing agent selected fromthe group consisting of an ethanolamine and N,N-dimethylformamide atboiling temperature for a period of time sufficient to solubilize andextract a whole undegraded pro tein component therefrom, the proportionof extractant to feathers ranging generally between 15 and 30 parts DMFper part feathers by weight and between about and 300 parts by weight offeathers per 1000 parts ethanolamine by volume, separating theproteincontaining solution from the insoluble residue, and

adding an effective amount of a surfactant to the solution whichsurfactant is selected from the group consisting of a cation-activesurfactant, an anion-active surfactant and a nonionic surfactant toprovide sudsing or lathering properties.

110. The method of claim 9 in which the solubilizing agent is anethanolamine and the surfactant is lauryl hydrogen sulfate.

11;. The method of claim 10 in which the ethanolamine istriethanolamine.

2. The composition of claim 1 in which the avian feathers are poultryfeathers.
 3. The composition of claim 1 in which the avian feathers arechicken feathers.
 4. An aqueous shampoo composition consistingessentially of a whole undergraded protein component of avian featherssufficient to impart manageability to hair, said protein component beingsoluble in a member selected from the group consisting of anethanolamine and N,N-dimethylformamide, a detergent surfactant selectedfrom the group consisting of a cation-active surfactant, a anion-activesurfactant and a nonionic surfactant to provide sudsing or latheringproperties, and water.
 5. The composition of claim 4, in which the avianfeathers are poultry feathers.
 6. The composition of claim 4 in whichthe avian feathers are chicken feathers.
 7. The composition of claim 4in which the ethanolamine is triethanolamine.
 8. The composition ofclaim 4 in which the surfactant is triethanolamine lauryl sulfate. 9.Method for the preparation of a shampoo concentrate comprising the stepsof treating avian feathers with a solubilizing agent selected from thegroup consisting of an ethanolamine and N,N-dimethylformamide at boilingtemperature for a period of time sufficient to solubilize and extract awhole undegraded protein component therefrom, the proportion ofextractant to feathers ranging generally between 15 and 30 parts DMF perpart feathers by weight and between about 150 and 300 parts by weight offeathers per 1000 parts ethanolamine by volume, separating theprotein-containing solution from the insoluble residue, and adding aneffective amount of a surfactant to tHe solution which surfactant isselected from the group consisting of a cation-active surfactant, ananion-active surfactant and a nonionic surfactant to provide sudsing orlathering properties.
 10. The method of claim 9 in which thesolubilizing agent is an ethanolamine and the surfactant is laurylhydrogen sulfate.
 11. The method of claim 10 in which the ethanolamineis triethanolamine.